Carbon monoxide conversion process



June 30, 1959 P. L. PAULL CARBON MONOXIOE CONVERSION PROCESS Fild Dec. 4, 1957 nited .States Patent() ,ssas'ss l CARBON MoNoxInli:A CONVERSION vrlzoc'uss Peter I.. Pauu, Westport,1cohn.,isssignoft Texaco Development Corporation, New York, N.Y., a corporationofDelaware s* Application December`4, 1957,Serial VNo. 700,594

S Claims. (Cl. A2li-213;)

This invention relates to a method and apparatus for the conversion of carbon monoxide-containing gases and steam to hydrogen. In one of its more specific aspects it is directed to a method of producing hydrogen from carbon monoxide-containing gases of variable sulfur content wherein the sulfur content of the feed gas is continuously maintained above a critical level.

The method of producing hydrogen' from carbon monoxide-containing gas bythe water-'gas shift conversion reaction is well known. In thewater-gas shift conversion process, carbon monoxide is reacted with steam vat a temperature within the range of about 600 F. .to about 1000 F. at a pressure from about atmospheric tofabout 650 p.s.i.g. in the presence-of an iron oxide or iron sul- -iide catalyst. The amount of steam employed may vary from the stoichiometric amount necessary lto react with the carbon monoxide, up to an excess of about Volumes offsteam per volume of carbon monoxide. Preferably about three to ve'volumes of steam are used for each volume of carbon monoxide. Iron water-gas shift conversion catalyst is usually'prepared from lhighly purified iron oxide with lesser-quantities of-the oxides of magnesium, potassium, sodium, aluminum, and chromium. These catalysts usually comprise ferrie oxide as manufactured, but are reduced to the ferrous form in use. When the gas processed in the water-gasshift conversion is substantially free of sulfur compounds,the liron oxide is reduced to a ferrous oxide form; When sulfur is present in significant quantities the iron oxideis reduced and suliided to the ferrous sulfide form. When the sulcontent of the feed gas varies overwide ranges, for example, when fuels free of sulfur are employed alternately with sulfur-containing-fuels, Ithe catalystfmay be alternatelyconverted to the oxide and the sulfide forms,

- Carbon monoxide-containinggases-for the production of hydrogen may be produced in various ways, forexample, by water-gas generation, steam-methane reform- 'fing and by the partial combustion of carbonaceous fuels. 4The partial combustion process has been developed 'as a highlyeicient and preferred method of producing -gases rich in hydrogen and-carbon monoxide. Although the process ofthis invention is applicableto the shift conversion of carbon monoxide-containing `gas fromany source, lit will be described hereinafter as applied to gases .produced by the partialoxidation. ofhydiocarbon vand' carbonaceous fuels. Carbon monoxide and hydrogen-containing gases produced by partial oxidation are vcommonly referred to 'as synthesis gas which'term will be used hereinafter. Synthesis gases producedl by par- 4tialoxidation vary greatly in the content of sulfur., For

example, natural gas is available in manyA areas! containinglittle or no sulfur. If-the natural 'gas i'sfree of sulfur, the synthesis gas produced therefromis also free to 4.0`w`eight 'percent or higher'. Synthesisgas vpro- A duced from sulfur-containing liquid and solid fuels there- 2,892,685 Patented June 30, 1959 fore contain a corresponding amount of sulfur. Frequently it is desirable to employ sulfur-free and sulfurcontaining fuels alternately for the production of synthesis gas for conversion to hydrogen, depending upon availability and cost. It has been observed that the alternate use of gaseous and liquid or solid fuels has been accompanied by disintegration of the shift conversion catalyst. Although it is not intended that the process of this invention be limited to any particular mechanism, it is postulated that the catalyst disintegration which has been observed is a result ofalternate sulfiding and oxidation of the shift conversion catalyst when feed stocks are employed containing varying amounts of sulfur. According to theprocess of this invention, disintegration of the catalyst is effectively prevented :by continuously maintaining the sulfur content ofthe feed gas above a critical level. The catalyst in either the suliided form or i11- the oxide form is equally satisfactory as a shift catalyst. 'Ihe shift conversion catalyst may be maintained in the suliided form by the addition of a minute amountof sulfur to sulfur-free feed gases. For example, at typical water-gas shift conversion conditions, the water-gas. shift catalyst may vbe maintained in the sulded condition if the gas feed at all times contains at least about 0.2 grain of sulfur per 100 standard cubic feet of feed gas. Although this amount of sulfur is eifective to prevent disintegration of the catalyst as a result of alternate oxidaion and sulding, the amount of sulfur appearing in the product gasis extremely small and may be completely removed when the hydrogen stream `is treated for carbon dioxide removal.

Sulfur-may be introduced into the shift conversion feed in numerous Ways. A convenient method of sulfur introduction is the injection of a gaseous sulfur compound, forvexample, hydrogen sulde, carbonyl sulfide or a mercaptan, directly into the shift conversion feed.

The sulfur content of the Water-gas shift feedrequired to maintain the iron catalyst in the sulfide form varies depending upon the amount of water vapor'in Ithe feed and the temperature of the shift conversion operation. These variables may he related in accordance with-the following equation to determine the sulfur contentl of the feed gas neededto maintain the catalyst in the sulde form: 1

where Sc is the critical level of sulfur expressed in grains per 100 standard cubic feet, T is the highest tempera- -ture prevailing in the shift conversion catalyst bed and W is the mol percent of water vapor in the shift conversion feed. The critical sulfur level for a wide range of shift conversion conditions varies from about 0.03 to about 0.7 .grain per hundred standard cubic feet and typically is below about 0.2 grain per hundred standard cubic feet.

An advantage of the process of this :invention -is that iron'shift conversion catalyst is maintained in sulfide form while alternately processing ,gas streams containing varying quantities of sulfur. Consequently, Ithe catalyst retains its strength and the increase in pressure drop which would otherwise result fromplugging of thefhed with disintegrated catalyst is avoided.

The accompanying drawing diagrammatically illustrates one form of the processV of this invention. Although the drawing illustrates one arrangement of appa- I ratus in which the process of this invention may be Aprac-` ticed, it is'not intended to limit the invention to the particular apparatus or materials described. Y

A fuel oil, for example, a diesel fuel oil, containing about 0.3 weightpercent sulfur, `in linev 10 is admixed with steam'from line 11 and passedthroughfeed manifold 12 to synthesis gas generator 13. Oxygen in line 14 is introduced into gas generator 13 wherein the oil, steam, and oxygen are reacted at an autogenous temperature of about 2600 F. Reaction products comprising carbon monoxide, hydrogen and small quantities of Vcarbon dioxide, water vapor, nitrogen, hydrogen sulide, and carbonyl suliide are withdrawn through line 16. 'YI-'he synthesis gas in line 16 is then passed through cooler 17, line 18, and admixed -with steam from line l19 to form a waterl gas shift conversion feed comprising about 50 percent water vapor at a temperature of about 750 F. and containing about 20Vgrains of sulfur per 100 standard cubic feet. The water-gas lshi-ft conversion feed is then passed through sulfur analyzer 20 wherein the stream is continuously analyzed for sulfur content. Responsive to the sulfur analysis obtained by sulfur analyzer 20, a signal is impressed upon control valve 22 in hydrogen sulfide line 23 to maintain valve 22 in a closed position. Water-.gas shift Vconversion feed containing about `2,0 grains per 100 standard cubic feet in line 24 is passed to water gasshift converter 26. In water-gas shift converter 26 the steam and carbon monoxide react in the presence of an iron shift conversion catalyst to produce hydrogen and carbon dioxide.

.Eluent product from Water gas shift converterw26 is withdrawn through line 27, cooler 28, and line 29 to separator 30. Water separated in Aseparator 30 is withdrawn vfor-disposal through line 32, and hydrogen-rich gas Vis withdrawn through line 33. Hydrogen-richgas in line 33 is passed to carbon dioxide removal unit 35 wherein carbon dioxide and sulfur-containing gases are separated by conventional means, for example byv extraction with ethanolamine. Hydrogen product is withdrawn for use through line 36 and carbon dioxide and sulfur compounds are withdrawn for disposal through line 37.

After processing diesel oil is describedabove, the oil and steam flows are discontinued and a substitute fuel freeof sulfur, for example, sweet natural gas is employed. In this case, natural gas in line 40 ispassed to `fuelfeed manifold 12 and thence to synthesisfgas generator 13. Sulfur-free reaction productsrin line v1,6,pass through cooler 17 ,and line 18. Steam from line l19 is admixed with the synthesis gas in line .18 to Vform a water-gas shift conversion feed containing aboutASO percent watervapor at a temperature of about 750 F. Watergas shift conversion feed is passed through sulfurvanalyzer 20 and line 24 to water-gas shift converterh26. Responsive to the sulfur analysis obtained by sulfur analyzer 20, a signal is impressed upon control valve 22. Valve 22-is opened admitting hydrogen sulfide at a controlled ratethrough line 23. Hydrogen sulfide is admixedwith the water-gas shift conversion feed to establish and maintain a sulfur concentration of about one grain of sulfur per hundred standard cubic feet. Water-gas shift conversion feed containing added sulfur is passed through line 24 to water-gas shift converter 26. The remaining operation is `effected in the same way as when diesel fuel koil is employed as fuel feed. The choice of fuel may be varied depending upon the relative availability of fuels at a given time. Obviously, hydrogen sulfide maybe separated from the carbon dioxide and. recycled for use in maintaining the sulfur levelof the vwater-gas shift converter feed above-the desired critical level. However, such a small quantity of hydrogen sulfide is used that it is generally preferred to employ hydrogen sulfide separated from streams which are more highly concentrated than the efiuent from carbon dioxide removal unit 35.

In a speciiic installation for the manufacture of yhydrogen by the water-gas shift conversion of a synthesis gas, `the following fuels are available for conversion to synthesis gas: A sweet natural gas freemof sulfuna diesel fuel oil containing 0.3 Weight percent sulfur `anda bunkerfuel oil containing.0.98 weight percentsulfur. Synthesis gases produced from the foregqingH-fuelshavethe analyses and sulfur contents set forth 1n the following tabulation:

Sweet Diesel Bunker Synthesis Gas Generator Fuel Natural Fuel Fuel Gas Oil Oil Sulfur, Weight, Percent None 0. 3 0. 98 Synthesis Gas, Analysis, yDry Basis, i mol Percent` .Carbon Monoxide 35. 9 45. 1 50. 5 `Hydrogen. L 50. 0 49. 0 .43.17 lCarbon Dioxide 1.` 9 0. 2 3. 9 Methane 0. 2k 0. 4` `(1.2 Nitrogen and Argon 2. 0 1. 3 1. 4 Sulunrgrlains perico se None 41 1142 Sweet natural gas is available as an interruptible supply and is used when available but when the supply is cut olf, the fuel requirements of the synthesis gas generator are supplied from afs'ource of diesel fuel oil. Ina 6 months period, ,sweet natural Vgas is employed, during 6 periods for a -total of 57 percent of the ,total operating time. ADuring theintervening periods when the ysweet natural gas is not available, diesel fuel oil isemployed for a Vtotal of 43 .percentof the total operating time. Synthesis gas from theforegoing fuels in admixturewith steamis contacted with va water-'gas shift conversion catalyst .for lthe production of additional hydrogen. Atthe beginning ofA this 6 months period, vfresh iron oxide cata- I lystis loaded tothetwater-gas .shift conversion reactor andthe pressure .drop through the reactor bed is about -l7rp.s.i.g. After V6 months operation, the pressure drop through` the .catalyst bed has risen to 147 p.s.i.g. The catalyst is unloaded andfoundto contain 17 percent fine materialwhich asbeen produced by catalyst disintegration.

ln-thisrsame installation, the foregoing fuels are employed ina subsequent 6 months period according to the method ofthis invention. -In this period, sweet natural gas is employed'as feed stock for 8 periods comprising 51 percent of the total operating time. interspersed with, the periods when sweet natural gas is employed, diesel fuel oil isvemployed for 6 periods comprising 35 percent of the total' operating time and'bunker fuel oil is employed for r4 periods during the remaining 14 percent of the operating time. During those periods when diesel fuel oil and'7'bunker-fuel oil are employed, the synthesis'gas produced contains more than the critical sulfur required to maintain the catalyst in a sulfided condition. During theperiods when sweet natural gas is employed, the synthesis gas produced contains no detectable sulfur. Duringtliese'periods, hydrogen suliideis continuously added to maintain the sulfur content of the synthesis gas above l grain per hundredstandard cubic feet. At ythe beginning of this 6 months period fresh iron oxide shift convertercatalystris loaded to the shift converter and the pressure drop through the reactor is about 17 p.s.i.g. After 6 months ofoperation, the pressure drop through the shift converter reactor has risen to `about 45 p.s.'i.g. At the conclusion `of 4the 6 months period, the shift converter catalyst is removed from the reactor and about 5 Algsercentof,the catalyst is found to have disintegrated or broken into'psmaller particles than those originally charged. vlt willbe noted by comparison of the above 6 months periods, that maintenance of at least l grainof sulfur .per hundred standard cubic feet in the synthesis gas substantially reduces the amount of catalyst disinte- "giation in the shift converterreactor so that catalyst disintegration and resultant vpressure drop increaseare. no longer important problems in the operation of thewatergas shiftreactor.

"' Obviousl many .modifications and `variations of.. the

v i.nirlrlentiori"as hereinbefore set forth may be made ,Without derartinsfrem the ,Spirit andswpe fhsreeflandely'seh inietiensfsherld beimppsed aser@ indieetsdlgin the arpsaeedfslaies- I claim:

l. In a water-gas shift process employing an iron catalyst wherein gases containing more and less sulfur than the amount necessary to maintain said iron catalyst in suliide form are processed, the improvement which comprises introducing hydrogen sulde into said gases containing less sulfur than the amount necessary to maintain said iron catalyst in sulfide form in an amount such that the sulfur content of the gases passed into contact with said catalyst is maintained continuously above the sulfur content necessary to maintain said catalyst in sulde form.

2. In a water-gas shift process employing an iron catalyst alternately to process gases containing more and less than the critical sulfur content Sc wherein said critical sulfur content Sc is related to the temperature of the shift converter catalyst and steam content of the shift converter feed by the equation where Sc is the critical level of sulfur expressed in 'grains per 100 standard cubic feet, T is the highest temperature prevailing in the shift conversion catalyst bed and W is the mol percent of water vapor in the shift conversion feed, the improvement which comprises introducing hydrogen sulde into said gases containing less than the critical sulfur content Sc in an amount such that the sulfur content of said gases is maintained continuously above said critical sulfur content Sc.

3. In a water-gas shift process wherein carbon monoxide and steam are contacted with an iron catalyst at a temperature within the range of about 600 to 1000 F. and with a feed ratio of steam to carbon monoxide within the range of about 1 mol of steam per mol of carbon monoxide to about mols of steam per mol of carbon monoxide, and varying in sulfur content greater and less than about 0.7 grain of sulfur per hundred standard cubic feet, the improvement which comprises introducing hydrogen sulfide into said gases containing less than about 0.7 grain of sulfur per hundred standard cubic feet in an amount such that the sulfur content of said gases is maintained continuously about 0.7 grain per hundred standard cubic feet.

4. In a water-gas shift process wherein carbon monoxide and steam are contacted with an iron catalyst at a temperature within the range of about 600 to 1000 F. and with a feed ratio of steam to carbon monoxide within the range of about 1 m01 of steam per mol of carbon monoxide to about 10 mols of steam per mol of carbon monoxide, and varying in sulfur content greater and less than about 0.7 grain of sulfur per hundred standard cubic feet, the improvement which comprises determining the sulfur content of said gases and adding hydrogen sulfide responsive to said determination in an amount such that the sulfur content is maintained continuously above 0.7 grain per hundred standard cubic feet.

5. A process for the conversion of fuels of varying sulfur content to hydrogen which comprises effecting partial combustion of a sulfur-containing carbonaceous fuel to produce a sulfur-containing synthesis gas comprising carbon monoxide, hydrogen and in excess of 0.7 grain hydrogen sulfide per hundred standard cubic feet, said hydrogen sulfide containing synthesis gas in admixture with steam, is contacted with an iron water-gas shift conversion catalyst to form additional hydrogen and carbon dioxide, thereafter discontinuing the partial combustion of said sulfur-containing fuel and effecting partial combustion of a carbonaceous fuel substantially free of sulfur to produce a low-sulfur synthesis gas comprising carbon monoxide, hydrogen and less than 0.7 grain of hydrogen sulde per hundred cubic feet, admixing hydrogen sullde to said low-sulfur synthesis gas to produce a water-gas shift conversion feed of a sulfur content in excess of 0.7 grain per hundred cubic feet, and contacting said watergas shift conversion feed in admixture 'with steam with said iron water-gas shift conversion catalyst to form additional hydrogen and carbon dioxide.

No references cited. 

1. IN A WATER-GAS SHIFT PROCESS EMPLOYING AN IRON CATALYST WHEREIN GASES CONTAINING MORE AND LESS SULFUR THAN THE AMOUNT NECESSARY TO MAINTAIN SAID IRON CATALYST IN SULFIDE FORM ARE PROCESSED, THE IMPROVEMENT WHICH COMPRISES INTRODUCING HYDROGEN SULFIDE INTO SAID GASES CONTAINING LESS SULFUR THAN THE AMOUNT NECESSARY TO MAINTAIN SAID IRON CATALYST IN SULFIDE FORM IN AN AMOUNT SUCH THAT THE SULFUR CONTENT OF THE GASES PASSED INTO CONTACT WITH SAID CATALYST IS MAINTAINED CONTINUOUSLY ABOVE THE SULFUR CONTENT NECESSARY TO MAINTAIN SAID CATALYST IN SULFIDE FORM. 